Asymmetric silicon-bridged metallocenes useful as catalysts in the polymerization of alpha-olefins, process for their preparation and use of said metallocenes for the polymerization of alpha-olefins

ABSTRACT

Novel asymmetric silicon-bridged metallocenes useful as catalysts in the polymerization of olefins and process for preparing said metallocenes.  
     The novel metallocenes are represented by the general formula (I):  
     (SiR′R″)(C p )(C p′ )MXX′  (I)  
     wherein  
     Cp is a partially or fully hydrogenated fluorenyl moiety selected from those of formula (II) and (III)  
                 
 
     Cp′ is an indenyl group selected from those of formula (IV)  
                 
 
     M represents a transition metal selected from Ti, Zr and Hf,  
     X and X′ represent, same or different from each other, a halogen atom,  
     R 1 ,R 2  and R 3  are, same or different from each other, an alkyl group containing 1 or 2 carbon atoms, an aryl group containing from  6  to  10  carbon atoms or a hydrogen atom,  
     (SiR′R″) is a divalent group which bridges the two groups C p  and C p ′  repectively on position  9  and  1 ,  
     R′ and R″ are, same or different from each other, an alkyl or aryl group containing from 1 to 10 carbon atoms.  
     Process for producing said metallocenes and process for the polymerization of α-olefins such as ethylene and propylene by means of said metallocenes.

TECHNICAL FIELD

[0001] The present invention relates to novel asymmetric silicon-bridged metallocenes useful as catalysts for the polymerization of α-olefins. It relates more specifically to novel silicon-bridged metallocenes containing an indenyl and a partially or fully hydrogenated fluorenyl moiety and to a process for their preparation. Finally it relates to a process for polymerization of α-olefins by using said asymmetric silicon-bridged metallocenes.

BACKGROUND OF THE INVENTION

[0002] Some asymmetric silicon-bridged metallocenes derived from group 4 metals and containing fluorenyl and indenyl moieties have already been proposed for the polymerization of α-olefins such as ethylene and propylene. For example, the use of silicon-bridged (9-fluorenyl)-(1-substituted indenyl) zirconium dichlorides in combination with aluminoxanes for the polymerization of α-olefins is disclosed in EP-A-0 754 698 and Macromolecules, 2000, 33 (5), 1546. However, the productivity and stability of such metallocenes remain insufficient.

[0003] Symmetric silicon-bridged bis(octahydrofluorenyl)zirconocenes and their use as catalysts for the polymerization of ethylene have been reported by Näsman et al. (J. Organomet. Chem., 1997, 545, 219) and are decribed in WO 95/27717. The latter also discloses the use of symmetric silicon-bridged bis(tetrahydrofluorenyl)zirconocenes. However, these zirconocenes are not suitable for the production of isotactic polypropylene.

[0004] Accordingly, there is still a need for silicon-bridged metallocene catalysts containing indenyl and fluorenyl moieties yielding very stereoregular polypropylene with high catalytic activity.

SUMMARY OF THE INVENTION

[0005] It is an object of the present invention to solve the above-mentioned problems by providing novel stable metallocenes useful as catalysts for α-olefin polymerization which are, in particular, able to produce, with a particularly high activity, polyethylene and highly stereoregular polypropylene and a process for preparing such metallocenes. It is another object of the present invention to provide a process for polymerization of the α-olefins by means of said metallocenes.

[0006] The invention is thus related to novel asymmetric silicon-bridged metallocenes of formula (I):

(SiR′R^(″)(C) _(p))(C_(p′))MXX′   (I)

[0007] wherein

[0008] C_(P) is a partially or fully hydrogenated fluorenyl moiety selected from those of formula (II) and (III)

[0009] C_(p′) is an indenyl group selected from those of formula (IV)

[0010] M represents a transition metal selected from Ti, Zr and Hf,

[0011] X and X′ represent, same or different from each other, a halogen atom,

[0012] R¹,R² and R³ are, same or different from each other, an alkyl group containing 1 or 2 carbon atoms, an aryl group containing from 6 to 10 carbon atoms or a hydrogen atom,

[0013] (SiR′R″) is a divalent group which bridges the two groups C_(p) and C_(p ′) repectively on position 9 and 1,

[0014] R′ and R″ are, same or different from each other, an alkyl or aryl group containing from 1 to 10 carbon atoms.

[0015] The invention also relates to a process for the preparation of these metallocenes.

[0016] Metallocenes of formula (I) wherein C_(p) is a tetrahydrofluorenyl group selected from those of formula (II) are preferably prepared by a route comprising the following steps:

[0017] a) production of 9-(1,2,3,4-tetrahydrofluorenyl)-1-(indenyl (or substituted indenyl))-dialkyl(or diaryl)silane from the (indenyl (or substituted indenyl))-dialkyl(or diaryl)-chlorosilane and 1,2,3,4-tetrahydrofluorenyllithium,

[0018] b) production of the dilithium salt of 9-(1,2,3,4-tetrahydrofluorenyl) (1-indenyl (or substituted indenyl))-dialkyl(or diaryl)silane precursor and

[0019] c) production of the metallocene by reacting the said dilithium salt with a halide of one of the transition metals mentioned hereabove.

[0020] Metallocenes of formula (I) wherein Cp is an octahydrofluorenyl group of formula (III) are preferably prepared by a route comprising the following steps:

[0021] a′) production of 9-(1,2,3,4,5,6,7,8-octahydrofluorenyl)-1-(indenyl (or substituted indenyl))-dialkyl(or diaryl)silane from (indenyl (or substituted indenyl))lithium and 9-(1,2,3,4,5,6,7,8-octahydrofluorenyl) dichloro-dialkyl (or diaryl)silane,

[0022] b′) production of the dilithium salt of 9-(1,2,3,4,5,6,7,8-octahydrofluorenyl)-1-(indenyl (or substituted indenyl))-dialkyl(or diaryl)silane precursor and

[0023] c′) production of the metallocene by reacting the said dilithium salt with a halide of one of the transition metals mentioned hereabove.

[0024] Finally the present invention relates to a process for polymerization of α-olefins by means of said metallocenes.

DETAILED DESCRIPTION

[0025] According to a first aspect, the present invention relates to novel stable metallocenes of the above general formula (I).

[0026] Preferably the transition metal is selected from hafnium and zirconium. Most preferably the transition metal is zirconium.

[0027] The halogen atoms X and X′ are preferably chlorine or bromine atoms and most preferably they are both chlorine atoms.

[0028] The group R¹ represents preferably a methyl group.

[0029] The groups R² and R³ represent preferably a methyl group, an aryl group containing from 6 to 10 carbon atoms or a hydrogen atom, with at least one of R² or R³ being different from hydrogen. Most preferably R² is a hydrogen atom and R³ is a phenyl group.

[0030] The groups R′ and R″ are preferably alkyl groups and more particularly alkyl groups containing from 1 to 3 carbon atoms. Most preferably R′ and R″ are a methyl group.

[0031] Among the most preferred metallocenes according to the present invention belongs the dimethylsilylene-[η5-1-(2-methyl-4-phenyl)indenyl]-[η5-9-(1,2,3,4,5,6,7,8-octahydrofluorenyl)] zirconium dichloride. Another example of most preferred metallocenes according to the present invention is the dimethylsilylene-[η5-1-(2-methyl-4-phenyl)indenyl]-[η5-9-(1,2,3,4-tetrahydrofluorenyl)] zirconium dichloride.

[0032] When used in combination with a cocatalyst, such as for example aluminoxane, said novel stable metallocenes are able to produce with a high activity polyethylene and highly stereoregular polypropylene.

[0033] According to a second aspect, the present invention relates to a process for producing the novel metallocenes of general formula (I) as described hereabove.

[0034] Preferably, step (a) is carried out by reacting the 1,2,3,4-tetrahydrofluorenyllithium with the chlorosilane in equimolar quantity.

[0035] Preferably, step (b) is carried out with at least two molar equivalents of butyllithium per mole of the 9-(1,2,3,4-tetrahydrofluorenyl)-1-(indenyl (or substituted indenyl))-dialkyl(or diaryl)-silane precursor, followed by reacting the obtained dilithium salt with one equivalent of transition metal halide.

[0036] Preferably, the step (a) is carried out in an inert solvent such as diethylether or a mixture of these, most often at about 0° C. At the end of the reaction, the suspension is usually hydrolyzed and the organic phase is isolated. After removal of the solvent, the 9-(1,2,3,4-tetrahydrofluorenyl)-1-(indenyl (or substituted indenyl))-dialkyl(or diaryl)-silane precursor is isolated.

[0037] Preferably, step (b) is carried out in an inert solvent, such as diethylether, hexane, pentane or tetrahydrofuran (THF) often at 0° C. The resulting lithium salt is advantageously separated from the solvent and washed prior to being reacted, in step (c), with about one equivalent of a transition metal halide selected from halides of Ti, Zr and Hf.

[0038] Step (c) is preferably carried out in an inert solvent, such as an ether, often at 0° C. After removal of the solvent, the solid metallocene of formula (I) wherein C_(p) is a group selected from those of formula (II) is isolated as a mixture of isomers.

[0039] Preferably, steps (a′), (b′) and (c′) are carried out in the same way as respectively the preferred steps (a), (b) and (c) for metallocenes of formula (I) wherein Cp is a group selected from those of formula (II). The 9-(1,2,3,4,5,6,7,8-octahydrofluorenyl)chloro-dialkyl(or diaryl)silane is generally synthesized as described in Organometallics, 1997, 16, 2503.

[0040] The novel metallocenes according to the present invention are useful as catalysts for the polymerization of α-olefins. The reaction is carried out by contacting said α-olefins with the said metallocene under polymerization conditions. It can be carried out in solution or in suspension in a hydrocarbon diluent or in suspension in one of the monomers maintained in the liquid form or in the gas phase. The polymerization conditions are well known by persons skilled in the art.

[0041] The metallocenes according to the invention can be used in combination with each other. They can also be used in combination with aluminoxanes. Methylaluminoxane (MAO) is preferred. They can also be used in combination with an ionizing agent. This ionizing agent can be chosen from the compounds comprising a first part which has the properties of a Lewis acid and which is capable of ionizing the metallocene and a second part that is inert towards the ionized metallocene. Examples of ionizing agents are triphenylcarbenium tetrakis(pentafluorophenyl) borate, N,N′-dimethylanilinium tetrakis(pentafluorophenyl) borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(pentafluorophenyl)boron, triphenylboron, trimethylboron, tri(trimethylsilyl)borate and organoboroxines.

[0042] Organometallic compounds are generally used as cocatalysts and/or poison scavengers. They can be selected from organometallic compounds of lithium, magnesium, zinc, aluminium or tin. The best results are obtained with organoaluminium compounds and in particular with trialkylaluminium compounds.

[0043] The α-olefins can be chosen from those containing up to 20, preferably up to 12 carbon atoms per molecule. The α-olefin is preferably ethylene or propylene. The metallocenes according to the present invention may be used for the homopolymerization of one of these α-olefins or for the copolymerization-random or block copolymerization-of one of these α-olefins with one or more comonomers. The preferred comonomers of ethylene are butene, hexene and their mixtures. The preferred comonomers of propylene are ethylene, butene and their mixtures.

[0044] The novel metallocenes according to the invention are stable molecules and are especially well adapted to polymerize with a particularly high activity ethylene and propylene, and are able to produce highly stereoregular polypropylene.

[0045] In addition to the foregoing description of the invention, the following examples are provided to illustrate the present invention.

[0046] In these examples reactions are carried out under an argon atmosphere using standard Schlenk techniques. Diethyl ether, THF, hexane and pentane were distilled from Na/K alloy under argon. Dichloromethane was distilled from CaH₂ under argon. MAO was purchased as a solution in toluene from Akzo Nobel and used as received. All other reagents were purchased from Aldrich and used without further purification.

[0047] Melting points (Tm) of the polymers were determined by DSC with a Perkin-Elmer DSC-System. ¹³C NMR spectra for pentad (mmmm in mol %) analysis were determined on an AMX500 spectrometer at 90° C. in C₆H₃Cl₃ with C₆D₆. Triad (mm in mol %) analysis was performed on ¹³C NMR spectra recorded on an AC-200 spectrometer at 120° C. in C₆H₃Cl₃ .¹H NMR spectra were recorded on a AC-200 spectrometer at room temperature in CDCl₃. Molecular masses were determined by High Resolution Mass Spectrometry (HRMS). The molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the polymers were determined by gel permeation chromatography (GPC-150C apparatus manufactured by Waters Co Ltd) recorded at 135° C. using a trichlorobenzene solution having a polymer concentration of 0.5 g/l and a polystyrene gel column, e.g. Waters Styragel HMW 6E available from Waters Co. Ltd.

1. PREPARATION OF METALLOCENES EXAMPLE 1 Preparation of the Dimethylsilylene-[η⁵-1-(2-Methyl-4-Phenyl)indenyl]-[η⁵-9-(1,2,3,4-Tetrahydrofluorenyl)] Zirconium Dichloride(Catalyst 1)

[0048] a) production of [1-(2-methyl-4-phenyl)indenyl]-[-9-(1,2,3,4-tetrahydrofluorenyl)]dimethylsilane

[0049] To a solution of 2.00 g (9.7 mmol) of 2-methyl-7-phenylindene in 40 ml of dry diethyl ether at 0° C. was added dropwise a 1.6 M solution of butyllithium in hexane (6.06 ml, 9.7 mmol). The solution was stirred at room temperature for 5 h. The solvent was removed under vacuum and the residue was washed twice with 20 ml of dry pentane. The anion was dried under vacuum, dissolved in 40 ml of dry diethyl ether and 5 ml dry THF, and then added dropwise via cannula to 2.36 ml (19.4 mmol) dichlorodimethylsilane in 20 ml of dry diethyl ether at 20° C. The addition was carried out over a 1 h period and the suspension was then stirred for 1 h at room temperature. The solvents and excess dichlorodimethylsilane were then removed under vacuum. The resulting oil was suspended in 30 ml of dry diethyl ether at 0° C. To this was added dropwise by cannula, one equivalent of 1,2,3,4-tetrahydrofluorenyllithium, prepared from 1.65 g (9.7 mmol) of 1,2,3,4-tetrahydrofluorene (prepared according to the method described by Colonge et al., Bull. Chim. Soc. Fr., 1953,75) and 6.06 ml (9.7 mmol) of butyllithium in 30 ml of dry ether and 10 ml of dry tetrahydrofuran. The suspension was allowed to stir overnight at room temperature and hydrolyzed with aqueous NH₄Cl. The organic phase was separated and the aqueous layer was extracted with ether. The combined organic phases were dried (MgSO₄), filtered and the solvent was removed. The oily residue was recrystallized from 100% ethanol to give 2.10 g of [1-(2-methyl-4-phenyl)indenyl]-[-9-(1,2,3,4-tetrahydrofluorenyl)]dimethylsilane (50%).

[0050] The compound was an oily solid that did not display a true melting point. ¹H NMR (CDCl₃):δ 7.57-7.11 (m, 12 H, arom), 6.78 (bs, 1 H Ind-C₅-sp²), 3.77 (bs, 1 H, Ind-C₅-sp³), 3.63 (bs, 1 H, THFlu-C₅-sp³), 2.54-2.42 (m, 4 H, CH₂), 2.20-2.17 (d, 3 H, CH₃), 1.95-1.55 (m, 4 H, CH₂) ,-0.26 (s, 3 H, Si-CH₃), -0.27 (s, 3 H, Si-CH₃). HRMS m/z for C₃₁H₃₂Si Calcd:432.2273, Found:432.2253.

[0051] b) production of the dilithium salt

[0052] To a solution of 0.50 g (1.16 mmol) of [1-(2-methyl-4-phenyl)indenyl]-[- 9-(1,2,3,4-tetrahydrofluorenyl)]dimethylsilane in 20 ml of dry diethylether at 0° C. was added dropwise two equivalents of a 1.6 M solution of butyllithium in hexane (1.45 ml, 2.32 mmol). The resulting suspension was stirred for 6 h at room temperature. The solvent was removed under vacuum and the residue was washed twice with 10 ml of dry pentane, giving a yellow solid.

[0053] c) production of dimethylsilylene-[η⁵-1-(2-methyl-4-phenyl)indenyl]-[η⁵-9-(1,2,3,4-tetrahydrofluorenyl)] zirconium dichloride

[0054] The yellow solid obtained in (b) was suspended in 20 ml of dry diethylether and cooled to 0° C. Zirconium tetrachloride (0.27 g, 1.16 mmol) was added as a solid. The orange suspension was stirred overnight at room temperature and the solvent was removed by filtration. The residue was extracted with dry methylene chloride. The solution was concentrated and stored at −20° C. to give 290 mg of dimethylsilylene-[η⁵-1-(2-methyl-4-phenyl)indenyl]-[η⁵-9-(1,2,3,4-tetrahydrofluorenyl)] zirconium dichloride an orange solid (42.2%), as a mixture of isomers (ca. 9:1). ¹H NMR (CDCl₃):δ 7.65-6.90 (m, 12 H, arom), 6.89 (s, 1 H, Ind-C₅-sp²), 3.04-2.55 (m, 4 H, CH₂), 2.34 minor, 2.23 major (s, 3 H, CH₃), 1.90-1.35 (m, 4 H, CH₂), 1.46 minor, 1.31-1.29 major, 1.19 minor (s, 6 H, Si-CH₃). HRMS m/z for C₃₁H₃₀SiCl₂Zr:Calcd:590.0541, Found: 590.0535.

EXAMPLE 2 Preparation of the Dimethylsilylene-[η⁵-1-(2-Methyl-4-Phenyl)Indenyl]-[η⁵-9-(1,2,3,4,5,6,7,8-Octahydrofluorenyl)] Zirconium Dichloride (Catalyst 2).

[0055] a′) production of [1-(2-methyl-4-phenyl)indenyl]-[-9-(1,2,3,4,5,6,7,8-octahydrofluorenyl)] dimethylsilane.

[0056] To a solution of 1.55 g (7.51 mmol) of 2-methyl-7-phenylindene in 30 ml of dry diethyl ether at 0° C. was added dropwise a 1.6 M solution of butyllithium in hexane (4.68 ml, 7.51 mmol). The solution was stirred at room temperature for 5 h. The solvent was removed under vacuum and the residue was washed twice with 20 ml of dry pentane.

[0057] The 2-methyl-7-phenylindenyllithium was dried under vacuum, dissolved in 30 ml of dry diethyl ether and 5 ml of dry THF and then added dropwise to 2.00 g (7.51 mmol) of 9-(chlorodimethylsilyl)-1,2,3,4,5,6,7,8-octahydrofluorene (prepared according to the method described by Marks et al., Organometallics, 1997, 16, 2503) in 20 ml of dry diethyl ether at −78° C. The mixture was allowed to warm to room temperature and stirred overnight to give a yellow suspension which was hydrolyzed with aqueous NH₄Cl. The organic phase was separated and the aqueous layer was extracted with ether. The combined organic phases were dried (MgSO₄), filtered and the solvent was removed. The oily residue was crystallized from 100% ethanol to give 1.85 g of [1-(2-methyl-4-phenyl)indenyl]-[-9-(1,2,3,4,5,6,7,8-octahydrofluorenyl)] dimethylsilane (56%). The compound was an oily solid that did not display a true melting point. ¹H NMR (CDCl₃):δ 7.52-7.15 (m, 8 H, arom), 6.79 (s, 1 H Ind-C₅-sp²), 3.74 (s, 1 H, Ind-C₅-sp³), 3.18 (bs, 1 H, OHFlu-C₅-sp³), 2.44-1.59 (m, 16 H, CH₂), 2.22 (s, 3 H, CH₃), -0.21 (s, 3 H,Si-CH₃), -0.25 (s, 3 H, Si- CH₃) HRMS m/z for C₃₁H₃₆Si: Calcd:436.2586, Found:436.2608.

[0058] b′) production of the dilithium salt and c′) production of dimethylsilylene-[η⁵-1-(2-methyl-4-phenyl)indenyl]-[η⁵-9-(1,2,3,4,5,6,7,8-octahydrofluorenyl)] zirconium dichloride.

[0059] Following the procedure of steps b) to c) of example 1, using (0.50 g. 1.14 mmol) of [1-(2-methyl-4-phenyl)indenyl]-[-9-(1,2,3,4,5,6,7,8-octahydrofluorenyl)] dimethylsilane prepared in step a′), 1.6 M butyllithium in hexane (1.43 mL, 2.28 mmol) and ZrCl4 (0.27 g, 1.14 mmol) gave 310 mg of dimethylsilylene-[η⁵-1-(2-methyl-4-phenyl)indenyl]-[η⁵-9-(1,2,3,4,5,6,7,8-octahydrofluorenyl)] zirconium dichloride 45.6%) as a yellow solid. ¹H NMR (CDCl₃):7.74-7.02 (m, 8 H, arom and 1 H, Ind-C₅-sp²), 2.76-1.20 (m, 16 H, CH₂), 2.30 (s, 3 H, CH₃), 1.17 (s, 3 H, Si-CH₃), 1.05 (s, 3 H, Si-CH₃). HRMS m/z for C₃₁H₃₄Cl₂SiZr:Calcd:594.0854, Found:594.0829.

2. POLYMERIZATION OF OLEFINS

[0060] General Conditions

[0061] A 250 ml crown capped glass pressure reactor containing 50 ml of toluene was equilibrated with the appropriate monomer at the desired temperature and pressure. The desired amount of methylaluminoxane (MAO) was added as a solution in toluene via syringe, and the solution was stirred for 5 min. 1 ml of the appropriate metallocene catalyst solution in toluene was added and the mixture was stirred until the desired reaction time was reached. The mixture was quenched with 2% HCl in methanol, filtered (or extracted in the case of atactic polypropylene), and dried in a vacuum oven at an appropriate temperature for the polymer sample.

EXAMPLES 3 and 4

[0062] These examples are related to the polymerization of ethylene under the general conditions described hereabove by using respectively catalyst 1 and catalyst 2 prepared in examples 1 and 2 respectively. The conditions are as follows:

[0063] Zr=5 μM, Al/Zr=4000:1 (atomic ratio), monomer pressure=15 psi

[0064] The duration of the polymerization was 6 min, the temperature was 50° C. The yield was 0.59 g for catalyst 1 (activity:8.6×10⁷ g polymer/(mol Zr.[ethylene]. h) (with [ethylene]=ethylene concentration in mol/l) and 0.65 g for catalyst 2 (activity:9.5×10⁷ g polymer/(mol Zr. [ethylene]. h).

COMPARATIVE EXAMPLE 5

[0065] Example 1 was repeated but the dimethylsilylene-(9-fluorenyl)-1-(2-methyl-4-phenyl)indenyl zirconium dichloride, preactivated for 10 minutes with 1 ml of MAO (catalyst 3), was used as catalyst.

[0066] The yield was 0.54 g (activity:7.9×10⁷ g polymer/(mol Zr. [ethylene]. h).

EXAMPLES 6 to 9

[0067] These examples are related to propylene solution polymerization in toluene according to the general procedure described hereabove using the catalysts described in examples 1 and 2 respectively. The conditions are as follows:

[0068] Zr=25 μM, Al/Zr=4000:1 (atomic ratio), monomer pressure=30 psi.

[0069] The duration of the polymerization was 60 minutes, and the temperature was 20° C. or 70° C.

[0070] The results are listed in Table 1. The activity is expressed in g polypropylene/(mol Zr.[propylene].h) (with [propylene]=propylene concentration in mol/l). TABLE 1 Temp Yield Example Catalyst (° C.) (g) Activity Tm (° C.) mmmm 6 1 20 18.0 1.40 × 10⁷ 118 84 7 1 70 16.0 9.00 × 10⁷ None 49 8 2 20 6.5 0.52 × 10⁷ 138 87 9 2 70 11.3 6.40 × 10⁷  81 56 10R 3 20 0.7 0.06 × 10⁷ 137 91 11R 3 70 0.8 0.43 × 10⁷ 135 89

COMPARATIVE EXAMPLE 10R

[0071] Example 6 was repeated, but using catalyst 3. The results are shown in table 1.

COMPARATIVE EXAMPLE 11R

[0072] Example 7 was repeated, but using catalyst 3. The results are shown in table 1.

EXAMPLES 12 and 13

[0073] These examples are related to the polymerization of ethylene using the catalysts described in examples 1 and 2. The polymerization conditions are as follows: Zr=2 μmol, in precontact with 2 ml MAO (10% by weight in toluene); monomer partial pressure=10 bars (solvent=hexane), MAO is used in a ratio Al/Zr of 15000:1, polymerization temperature=70° C., duration=1 h. The activity of the catalyst is expressed in g of polyethylene/mol Zr* hour.

[0074] The results of these tests are given in table 2 below. TABLE 2 Yield Example Catalyst Temp. (° C.) (g) Activity Tm (° C.) 12 1 70 185  9.25 × 10⁷ 129 13 2 70 245 12.25 × 10⁷ 115   14R 3 70  82  8.20 × 10⁷ —

COMPARATIVE EXAMPLE 14R

[0075] Example 12 was repeated but using 1 μmol of catalyst 3 in precontact with 1 ml of MAO, and isobutane as solvent. The results are reported in table 2.

EXAMPLE 15 and 16

[0076] These examples are related to propylene bulk polymerization with catalyst 1 and 2 according to the following general procedure: the polymerization run is carried out in a 5 liter stainless steel reactor. Cocatalyst (MAO, 10% by weight in toluene, 45 ml), catalyst (5 μmol Zr in precontact with 5 ml MAO, 10% by weight in toluene), Al/Zr=15,000:1 (molar ratio), and liquid propylene (3.5 liters) are successively introduced under argon blanket and heated to the polymerization temperature (70° C.). The polymerization conditions are maintained for 60 minutes. The polymerization is then stopped by simultaneously flashing the residual monomer and cooling down the reactor.

[0077] The results of the polymerization trials are shown in table 3 below. The activity of the catalyst is expressed in g of polypropylene/mol Zr* hour. TABLE 3 Temp. Tm Mw Ex. Catalyst (° C.) Yield (g) Activity (° C.) mm (daltons) Mw 15 1 70 309  6.18 × 10⁷ 139.7 85 16000 2.6 16 2 70 529 10.58 × 10⁷ 125.9 91 27000 1.9 

1- Novel asymmetric silicon-bridged metallocenes useful as catalysts in the polymerization of olefins represented by the general formula (I): (SiR′R″)(C_(p))(C_(p′))MXX′  (I) wherein Cp is a partially or fully hydrogenated fluorenyl moiety selected from those of formula (II) and (III)

Cp′ is an indenyl group selected from those of formula (IV)

M represents a transition metal selected from Ti, Zr and Hf, X and X′ represent, same or different from each other, a halogen atom, R¹,R² and R³ are, same or different from each other, an alkyl group containing 1 or 2 carbon atoms, an aryl group containing from 6 to 10 carbon atoms or a hydrogen atom, (SiR′R″) is a divalent group which bridges the two groups C_(p) and C_(p′) repectively on position 9 and 1, R′ and R″ are, same or different from each other, an alkyl or aryl group containing from 1 to 10 carbon atoms. 2- Novel asymmetric silicon-bridged metallocenes according to claim 1 wherein the transition metal is zirconium. 3- Novel asymmetric silicon-bridged metallocenes according to claim 1 wherein X and X′ are both chlorine atoms, and R′ and R″ are both methyl groups. 4- Novel asymmetric silicon-bridged metallocene according to claim 1 wherein R¹ is a methyl group, R² and R³ are a methyl group, an aryl group containing from 6 to 10 carbon atoms or a hydrogen atom, with at least one of R² or R³ being different from hydrogen. 5- A novel asymmetric silicon-bridged metallocene according to claim 1, which is dimethylsilylene-[η⁵-1-(2-methyl-4-phenyl)indenyl]-[η⁵-9-(1,2,3,4-tetrahydrofluorenyl)] zirconium dichloride. 6- A novel asymmetric silicon-bridged metallocene according to claim 1, which is dimethylsilylene-[η⁵-1-(2-methyl-4-phenyl)indenyl]-[η⁵-9-(1,2,3,4,5,6,7,8-octahydrofluorenyl)] zirconium dichloride. 7- Process for producing novel metallocenes according to claim 1 and corresponding to the general formula (I) wherein C_(p) is a tetrahydrofluorenyl moiety of formula (II) comprising the following steps: a) production of 9-(1,2,3,4-tetrahydrofluorenyl)-1-(indenyl (or substituted indenyl))-dialkyl(or diaryl)silane from the (indenyl (or substituted indenyl))-dialkyl(or diaryl)-chlorosilane and 1,2,3,4-tetrahydrofluorenyllithium, b) production of the dilithium salt of 9-(1,2,3,4-tetrahydrofluorenyl) (1- indenyl (or substituted indenyl))-dialkyl(or diaryl)silane precursor and c) production of the metallocene by reacting the said dilithium salt with a halide of Ti, Zr and Hf. 8- Process for producing novel metallocenes according to claim 1 and corresponding to the general formula (I) wherein C_(p) is an octahydrofluorenyl moiety of formula (III) comprising the following steps: a′) production of 9-(1,2,3,4,5,6,7,8-octahydrofluorenyl)-1-(indenyl (or (substituted indenyl))-dialkyl(or diaryl)silane from (indenyl (or substituted indenyl))lithium and 9-(1,2,3,4,5,6,7,8-octahydrofluorenyl) dichloro-dialkyl(or diaryl)silane, b′) production of the dilithium salt of 9-(1,2,3,4,5,6,7,8-octahydrofluorenyl)-1-(indenyl (or substituted indenyl))-dialkyl(or diaryl)silane precursor and c′) production of the metallocene by reacting the said dilithium salt with a halide of one of Ti, Zr and Hf. 9- Process for the polymerization of α-olefins by means of the metallocenes according to claim
 1. 10- Process according to claim 9 applied to the polymerization of ethylene or propylene. 